JP3216466B2 - Rubber-modified thermoplastic resin and composition thereof - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION The present invention relates to
The present invention relates to a rubber-modified thermoplastic resin suitable for imparting excellent performance, and a composition comprising the rubber-modified thermoplastic resin and another thermoplastic resin.

[0002]

2. Description of the Related Art ABS resins and AES resins are widely known as rubber-modified thermoplastic resins, and are used in large quantities industrially. As a method for producing an ABS resin, the following two methods are generally known. A method obtained by polymerizing 75 to 95% by weight of a monomer composed of styrene and acrylonitrile in the presence of 5 to 25% by weight of a rubbery polymer. A high rubber content ABS resin (hereinafter referred to as "Rubber-rich AB") obtained by polymerizing 55 to 60% by weight of a monomer composed of styrene and acrylonitrile in the presence of 40 to 45% by weight of a rubbery polymer.
S resin)), separately obtained styrene-
A method of obtaining an ABS resin by blending it with an acrylonitrile copolymer (AS resin) and adjusting the content of the rubbery polymer in the blend to 5 to 25% by weight (A obtained by this method)
The BS resin is hereinafter referred to as “blend type ABS resin”). According to the above-mentioned method, various kinds of ABS resins having different qualities can be produced with high productivity by appropriately selecting the amount of the rubber-rich ABS resin and appropriately selecting the type of the AS resin.

However, in the ABS resin industry, further cost reduction is required. As a countermeasure for this cost reduction, there is a method of further increasing the rubber content of the rubber-rich ABS resin and increasing the blending amount of the low-cost AS resin with excellent productivity to increase the productivity of the blend type ABS resin. Conceivable. However, according to our study, when the rubber content of the rubber-rich ABS resin is increased compared to the conventional product, the blend type ABS resin using the resin has a remarkable phenomenon that fish eyes are generated, and the appearance of the molded product is poor. Type AB using conventional rubber-rich type ABS (resin) with high resistance and impact resistance
Inferior to S resin. The rubber-rich ABS resin is
It is used by being blended with other thermoplastic resins in addition to the S resin. However, when the rubber content of the rubber-rich ABS resin is increased, the same problems as described above were observed.

[0004]

SUMMARY OF THE INVENTION The present invention is directed to a rubber-rich ABS resin having a high rubber content, which solves the above-mentioned problems of a rubber-rich ABS resin having a high rubber content, and a rubber-rich ABS resin and other rubber-rich ABS resins. An object is to provide a thermoplastic resin composition comprising a thermoplastic resin.

[0005]

Means for Solving the Problems The present inventors have made intensive studies on solving the above-mentioned problems caused by the rubber-rich ABS resin. As a result, the rubber-rich A having a rubber content of 52 to 75 % by weight was obtained.
Q value of BS resin is 120 × 10 ^{-4 to} 500 × 10 ^-4 ml
Per second, it has been found that the above-mentioned problems can be solved by reforming, and the present invention has been achieved. That is,
The present invention is obtained by polymerizing an aromatic vinyl compound (b) and a vinyl cyanide compound (c) in the presence of a rubbery polymer (a) component, and the content of the component (a) is 52 to 75% by weight. %, The content of the component (b) is 5 to 46 % by weight, the content of the component (c) is 2 to 43 % by weight, and the following Q value is 120 × 10 ^−4.
The present invention provides a rubber-modified thermoplastic resin characterized by having a graft ratio of not more than 500 × 10 ⁻⁴ ml / sec and a graft ratio of 5% by weight or more. Q value: Shimadzu flow tester (CAPILLARY RH
Using EOMETER CFT-500), the volume per second (ml / sec) obtained by melting and extruding the sample under the following measurement conditions Measurement conditions: Sample amount: 1.8 g Plunger area: 1.0 cm ² die Size: 2.0 mm length × 1.0 mmφ Preheating temperature and time: 200 ° C. × 5 minutes Measurement temperature: 200 ° C. Load: 60 kg / cm ² (However, the sample to be measured is at 110 ° C. × 60 minutes. The volatile substance content is adjusted to 0.1% by weight or less.) The present invention also relates to a composition comprising the rubber-modified thermoplastic resin (A) and another thermoplastic resin (B). Provided is a thermoplastic resin composition in which the content of the component (a) is 3 to 35% by weight.

Hereinafter, the present invention will be described in detail. The rubber-modified thermoplastic resin (A) of the present invention is obtained by polymerizing an aromatic vinyl compound (b) and a vinyl cyanide compound (c) in the presence of a rubber-like polymer (a) component. The content of the component (a) in the thermoplastic resin (A) is 52
75 % by weight, the content of the component (b) is 5 to 46 % by weight,
(C) The content of the component is 2 to 43 % by weight, and the Q value is 12
0 × 10 ^{−4 to} 500 × 10 ⁻⁴ ml / sec, graft rate 5
It is a rubber-modified thermoplastic resin of not less than weight%.

The rubbery polymer of the component (a) used in the present invention includes, for example, polybutadiene, polyisoprene, styrene-butadiene copolymer (styrene content 5 to 5).
60% by weight), styrene-isoprene copolymer, acrylonitrile-butadiene copolymer, ethylene-α-olefin-based copolymer, ethylene-α-olefin-polyene copolymer, acrylic rubber, butadiene-
(Meth) acrylate copolymer, polyisoprene, styrene-butadiene block copolymer, styrene-isoprene block copolymer, hydrogenated styrene-butadiene block copolymer, hydrogenated butadiene-based polymer,
Ethylene ionomers and the like can be mentioned. In addition, the styrene-butadiene block copolymer and the styrene-isoprene block copolymer include those having an AB type, ABA type, a taper type, a radial teleblock type, and the like. Furthermore, the hydrogenated butadiene-based polymer has, in addition to the hydride of the above block copolymer, a styrene block and a styrene-butadiene random copolymer block, a 1,2-vinyl bond content in polybutadiene. A hydride of a polymer comprising a block of not more than 20% by weight and a polybutadiene block having a 1,2-vinyl bond content of more than 20% by weight is included. These rubbery polymers are used alone or in combination of two or more.
The preferred component (a) is at least one conjugated diene rubber selected from polybutadiene and styrene-butadiene (preferably 5 to 60% by weight of styrene) copolymer, and more preferably polybutadiene / styrene-styrene. Butadiene copolymer: 50-99 / 1-50
(% By weight).

As the aromatic vinyl compound as the component (b), for example, styrene, t-butylstyrene, α-methylstyrene, p-methylstyrene, divinylbenzene,
1,1-diphenylstyrene, N, N-diethyl-p-
Aminoethylstyrene, N, N-diethyl-p-aminomethylstyrene, vinylpyridine, vinylxylene, monochlorostyrene, dichlorostyrene, monobromostyrene, fluorostyrene, ethylstyrene, vinylnaphthalene, etc., and particularly styrene, α- Methylstyrene is preferred. These aromatic vinyl compounds may be used alone or in combination of two or more.

Examples of the vinyl cyanide compound as the component (c) include acrylonitrile and methacrylonitrile.

For the purpose of the present invention, other monomers can be used as long as they do not hinder. As other monomers, for example, methyl acrylate, ethyl acrylate,
Acrylates such as propyl acrylate, butyl acrylate, amyl acrylate, hexyl acrylate, octyl acrylate, 2-ethylhexyl acrylate, cyclohexyl acrylate, dodecyl acrylate, octadecyl acrylate, phenyl acrylate, benzyl acrylate; methyl methacrylate, ethyl methacrylate, propyl methacrylate;
Butyl methacrylate, amyl methacrylate, hexyl methacrylate, octyl methacrylate, 2-ethylhexyl methacrylate, cyclohexyl methacrylate, dodecyl methacrylate, octadecyl methacrylate, phenyl methacrylate, methacrylic acid esters such as benzyl methacrylate; maleic anhydride, itaconic anhydride, citraconic anhydride and the like Unsaturated acid anhydrides; unsaturated acids such as acrylic acid and methacrylic acid; maleimide, N-methylmaleimide, N-butylmaleimide;
Α- such as N- (p-methylphenyl) maleimide, N-phenylmaleimide and N-cyclohexylmaleimide
Or an imide compound of β-unsaturated dicarboxylic acid (also referred to as a maleimide monomer); glycidyl methacrylate;
Epoxy compounds such as allyl glycidyl ether; unsaturated carboxylic amides such as acrylamide and methacrylamide; acrylamine, aminomethyl methacrylate,
Amino group-containing unsaturated compounds such as aminoethyl methacrylate, aminopropyl methacrylate, aminostyrene,
3-hydroxy-1-propene, 4-hydroxy-1-
Butene, cis-4-hydroxy-2-butene, trans-4-hydroxy-2-butene, 3-hydroxy-2-
Examples include a hydroxyl group-containing unsaturated compound such as methyl-1-propene, 2-hydroxyethyl acrylate, and 2-hydroxyethyl methacrylate; and an oxazoline group-containing unsaturated compound such as vinyl oxazoline. These monomers are used alone or in combination of two or more. The content of the other monomer is preferably 20% among the components excluding the component (a).
% By weight, more preferably 10% by weight or less.

The content of the component (a) in the rubber-modified thermoplastic resin (A) is 52 to 75% by weight, preferably 56 to 74% by weight.
% By weight. Is less than content 52% by weight of component (a), the effect of improving the productivity is insufficient, whereas, 75 wt%
If the ratio exceeds the above range, the generation of fish eyes increases, and the appearance and impact resistance are greatly reduced. The content of the component (b) in the rubber-modified thermoplastic resin (A) is 5 to 46% by weight,
Preferably it is 13 to 41% by weight. The content of the component (c) is 2 to 43% by weight, preferably 3 to 31% by weight. When the component (b) is less than 5% by weight, the content of the component (b) is 4 %.
When the content exceeds 6 % by weight, when the component (c) is less than 2% by weight, and when the component (c) exceeds 43 % by weight, the effect of improving the poor phenomenon of fish eye generation and the appearance are improved. At least one of the improvement effect and the impact resistance improvement effect is not sufficient, and the three cannot be maintained at the desired levels.

The Q value of the rubber-modified thermoplastic resin (A) is 1
It is 20 × 10 ^{−4 to} 500 × 10 ⁻⁴ ml / sec. Even if the Q value is less than 120 × 10 ⁻⁴ ml / sec, 500 × 10 4
Even when the amount exceeds ^-4 ml / sec, fish eyes are often generated, the appearance is poor, and the impact resistance is not sufficient. The measurement conditions for the Q value are as described above.

The graft ratio of the rubber-modified thermoplastic resin (A) is at least 5% by weight, preferably at least 10% by weight.
When the graft ratio is less than 5% by weight, fish eyes are often generated, and the appearance and impact resistance are poor. The graft ratio is
It is measured by the following method. Here, the graft ratio refers to the ratio of the copolymer component directly graft-bonded to the rubber-like polymer with respect to the amount of rubber in the rubber-modified thermoplastic resin. This graft ratio can be controlled by the amount of the polymerization initiator, the polymerization temperature, and the like. A specific method of obtaining the graft ratio is as follows. First, 2 g of the rubber-modified thermoplastic resin (A) of the present invention is charged into acetone at room temperature, and sufficiently stirred to obtain an insoluble matter (w).
Ask for. On the other hand, the amount of the rubbery polymer in the insoluble matter (w) can be calculated based on the polymerization recipe. With the calculated total amount of the rubbery polymer as R, the graft ratio is determined from the following equation. Graft ratio (% by weight) = [(w−R) / R] × 100

The content of the component (a), the component (b) and the component (c) in the rubber-modified thermoplastic resin (A) can be properly adjusted by adjusting the amounts of these components during polymerization. Further, their contents can be determined by a known quantitative analysis method. The Q value of the rubber-modified thermoplastic resin (A) is adjusted by appropriately selecting the type and amount of a chain transfer agent and an initiator used during polymerization, by appropriately selecting the polymerization temperature, and by adjusting the rubber of component (a). It can be carried out by appropriately selecting the gel content and the molecular weight of the polymer in the form. Rubber-modified thermoplastic resin (A)
Examples of the production method include a solution polymerization method, a bulk polymerization method, a suspension polymerization method, an emulsion polymerization method, and a method combining these methods. A preferred polymerization method is an emulsion polymerization method, and generally known polymerization auxiliaries used in the emulsion polymerization method can be used.

Examples of the polymerization initiator used in the production of the rubber-modified thermoplastic resin (A) of the present invention include various organic peroxides such as hydroperoxides, alkyl peresters and percarbonates, preferably cumene hydroperoxide. Oxide, diisopropylbenzene hydroperoxide, and t-butylperoxyisopropyl carbonate. In particular, when t-butyl peroxyisopropyl carbonate is used, the effect of the present invention can be further improved. The preferred amount of the initiator is 0.1 to 100 parts by weight of the total of the rubber component and the monomer component.
2 parts by weight.

Examples of the chain transfer agent include halogenated hydrocarbons (eg, chloroform, bromoform, etc.) and mercaptans (eg, n-dodecyl mercaptan, t-dodecyl mercaptan, n-octyl mercaptan, n-hexadecyl mercaptan, etc.). Terpenes (eg, dipentene, terpinolene, etc.) and α-methylstyrene dimer.

The other thermoplastic resin (B) which is mixed with the rubber-modified thermoplastic resin (A) is, for example,
ABS resin / A having a rubbery polymer content of less than 50% by weight
ES resins, AAS resins, AS resins, styrene resins such as HIPS, PS; olefin resins such as polyethylene and polypropylene; PA6, PA66, PA46, P
Polyamide resins such as A12; Polyester resins such as polybutylene terephthalate, polyethylene terephthalate, and polyarylate; Polyphenylene ether-based resins such as polycarbonate resin, polyphenylene ether or polyphenylene ether / styrene-based resin; Polyacetal, vinyl chloride resin, polysulfone, PPS,
There are polyether sulfone, ethylene-vinyl acetate copolymer, EVOH and the like, and these can be used alone or in combination of two or more.

Other preferable thermoplastic resins (B) include the following a. , B. Each alone or a. And b.
In combination. a. A monomer comprising at least two groups selected from the group consisting of an aromatic compound, a vinyl cyanide compound, a (meth) acrylate ester and a maleimide monomer in the presence of a rubber-like polymer; And a rubber-modified thermoplastic resin having a rubbery polymer content of less than 50% by weight. Here, the rubbery polymer and the monomer include those described above. Further, the intrinsic viscosity (at 30 ° C. in methyl ethyl ketone) of the methyl ethyl ketone-soluble component of the rubber-modified thermoplastic resin is preferably from 0.2 to 1 dl / g, more preferably from 0.3 to 0.6 dl / g. b. An aromatic vinyl compound, a vinyl cyanide compound,
It is obtained by polymerizing at least two kinds of monomers selected from the group of (meth) acrylic acid esters and maleimide monomers, and has an intrinsic viscosity (measured at 30 ° C. using methyl ethyl ketone as a solvent). Preferably 0.2-1.3d
1 / g, more preferably 0.3 to 1.0 dl / g, particularly preferably 0.35 to 0.7 dl / g.

The above a. As, for example, ABS resin,
AES resin, AAS resin, MBS resin and the like,
Among them, ABS resin and AES resin are preferred. B. Examples thereof include the following copolymers. I. A copolymer of an aromatic vinyl compound and a vinyl cyanide compound. A preferable composition ratio is such that the former monomer is 50 to 99.
% Polymerization, the latter being 1 to 50% by weight. B. Copolymer of aromatic vinyl compound and (meth) acrylate. C. Aromatic vinyl compound, maleimide monomer and, if necessary, vinyl cyanide compound and / or (meth)
A copolymer composed of acrylic acid esters. In addition, an unsaturated acid anhydride monomer is used in place of the maleimide-based monomer, the obtained copolymer is imidized, and the obtained post-imide type copolymer is also included herein. The aromatic vinyl compound, vinyl cyanide compound, (meth) acrylic acid ester, and maleimide-based monomer here are the same as those described above.

The composition ratio of each component in the thermoplastic resin composition according to claim 2 comprising the rubber-modified thermoplastic resin (A) and the other thermoplastic resin (B), is as follows. The respective components are appropriately blended so that the rubbery polymer as the component (a) is preferably contained in the composition at 3 to 35% by weight. More preferably, the content of the component (a) is 5 to 25% by weight. If the content of the component (a) is less than 3% by weight, sufficient impact resistance cannot be obtained. On the other hand, if it exceeds 35% by weight, the molded article becomes soft, which is not preferable. When a rubber-modified thermoplastic resin (C) other than the rubber-modified thermoplastic resin (A) of the present invention is used as the other thermoplastic resin (B), it is contained in the rubber-modified thermoplastic resin (C). The handling of the rubbery polymer (hereinafter referred to as “a ′ component”) is as follows. a 'component is also a
It shall be regarded as a component and satisfy the following conditions. That is, the content of (a + a ') is 3 to 35% by weight, and the content of a is 3 to 35% by weight. Preferably, (a +
a ') The content is 5 to 25% by weight, and the content of a is 5 to
25% by weight.

The thermoplastic resin composition according to claim 2 of the present invention comprises a rubber-modified thermoplastic resin (A) and a thermoplastic resin (B).
And, if necessary, kneaded with various additives. As a kneading method, there is a method using an extruder, a roll, a Banbury mixer, a kneader, or the like. A preferable method is a method using an extruder, and examples of the extruder include a single screw extruder and a twin screw extruder.

In kneading the various components using the above-described kneading method, all the components may be kneaded at once, or some of the components may be kneaded first, and the remaining components may be kneaded or divided. May be added and kneaded. Various additives can also be added to the rubber-modified thermoplastic resin (A), if necessary. When kneading is required, kneading can be performed by the method described above. Examples of various additives include known colorants, pigments, lubricants, weathering agents, antistatic agents, antioxidants, flame retardants, heat aging inhibitors, plasticizers, antibacterial and antifungal agents, and the like.

The thermoplastic resin composition according to claim 2 of the present invention can be obtained by injection molding, sheet extrusion, vacuum molding, profile extrusion,
Various molded products can be molded by injection press, foam molding, blow molding, hollow molding and the like.

[0024]

〔Evaluation method〕

(1) Measurement of Q value It was described in the above text. (2) Method of mixing rubber-modified thermoplastic resin (A) and thermoplastic resin (B) A rubber-modified thermoplastic resin (A), a thermoplastic resin (B), and an additive were mixed in a Henschel mixer at a ratio shown in Table 2. The mixture was mixed using an extruder having a cylinder set temperature of 200 ° C. to obtain pellets. (3) Method of Forming Test Piece A test piece for measuring gloss and a test piece for measuring Izod impact strength were molded under the following molding conditions using the pellet obtained by the method of (2) above as a molding material. Molding machine: 5 oz. In-line screw type molding machine Mold temperature: 50 ° C. ± 5 ° C. Molding machine setting conditions; Cylinder set temperature: 200 ° C. Injection pressure: Primary pressure 75 to 95 kg / cm ² G, secondary pressure 5
0 kg / cm ² G Back pressure 5 kg / cm ² G Molding cycle: Injection 15 seconds, loading 10 seconds, curing 40 seconds, cycle start 2 seconds (4) Measurement of glossiness Digital variable-angle gloss meter (Suga Test Machine Co., Ltd. ) DIGIT
AL VARIABLE GLOSS METER U
GV-5D), the incident angle and the light receiving angle were measured at 45 ° C. (5) Measurement of Izod impact strength ASTM D256 (1/4 ", with notch, unit = kg)
f · cm / cm). (6) Fish Eye Measurement A sheet sample for fish eye measurement was prepared by the following method, and the fish eye was measured. A 50-ton press machine heated at 220 ° C. is prepared. The pellet obtained by the above method (2) is placed on a SUS mold plate (30 cm × 3
(0 cm × 0.5 mm) (10 to 15 g). It is sandwiched between presses as it is, and a pressure of 0 to 0.5 kg / cm ² G is applied, and the mixture is heated for 5 minutes. The pressure is slowly applied (up to 10 kg / cm ² G), and the pellet sample (molten) that has protruded from between the mold plates is slowly pulled out. The sample is drawn out in the form of a film, and is drawn out at a thickness of about 10 to 30 μm as thin as 1 m or more. A 3.57 cm diameter circle (area 10c) was placed on the film sample.
m ² ) and count the fish eyes in the circle (0.2 mm or more in diameter). The above is performed at three points, and the total is divided by the area to obtain the number per 1 cm ² , which is evaluated as fisheye.

Reference Example 1. Rubber-modified thermoplastic resin (A)
Of the production method] in the flask, and 60 parts of a polybutadiene rubber latex in terms of solid content, a styrene - mixed rubbery polymer and 10 parts butadiene copolymer rubber latex in terms of solid content
60 parts of latex is added in terms of solid content , and ion-exchanged water 1
50 parts, 7 parts of styrene, 3 parts of acrylonitrile, and 0.2 part of t-dodecyl mercaptan were further added to raise the temperature in the flask to 60 ° C., and then 0.2 parts of sodium pyrophosphate and ferrous sulfate heptahydrate A solution prepared by dissolving 0.01 part of the product and 0.4 part of glucose in 20 parts of ion-exchanged water is added.
The polymerization was started by further adding 0.1 part of cumene hydroperoxide, and the temperature of the hot bath was maintained at 70 ° C. After polymerization for 1 hour, 21 parts of styrene, 9 parts of acrylonitrile,
0.5 parts of t-dodecyl mercaptan and 0.2 parts of cumene hydroperoxide were continuously added over 2 hours,
Polymerization was further carried out for 1 hour to complete the reaction. The obtained copolymer latex was coagulated using sulfuric acid, washed with water and dried. ABS-1 shown in the table was obtained.

[0026]

[Table 1]

ABS-2 and ABS-4 in Table 1 represent A
Polymerization was carried out under the same conditions as ABS-1 and ABS-3 except that t-butylperoxyisopropyl carbonate was used instead of cumene hydroperoxide of BS-1 and ABS-3. ABS-3,5,
Nos. 6, 7, and 8 are ABS-1 formulations, which were carried out under the same conditions as ABS-1 except that the amount of rubber and the amount of t-dodecylmercaptan were appropriately changed.

(Thermoplastic resin) AS-1: a copolymer of 75% styrene and 25% acrylonitrile, [η] (intrinsic viscosity of a bath of methyl ethyl ketone) 0.4 dl / g AS-2; styrene 75 % And acrylonitrile 25%, [η] is 0.6 dl / g AS-3; styrene 70% and acrylonitrile 30% copolymer, [η] is 0.7 dl / g

Examples 1 to 5 Examples 1 to 5 are thermoplastic resin compositions using a rubber-modified thermoplastic resin having a Q value within the range of the present invention. Table 2 shows the formulation and evaluation results.

[0030]

[Table 2]

Comparative Examples 1 to 7 Comparative Examples 1 to 7 are thermoplastic resin compositions using a rubber-modified thermoplastic resin having a Q value outside the range of the present invention. Table 2 shows the formulation and evaluation results.

Examples 1 to 5 are excellent in the gloss and impact resistance of the molded product, and are also improved in the occurrence of fish eyes, as is clear from comparison with Comparative Examples 1 to 7.

[0033]

The rubber-modified thermoplastic resin of the present invention (A)
The molded product obtained by blending with other thermoplastic resin (B) has excellent gloss and impact resistance, and has a remarkable phenomena of fish eye generation even if it has a high rubber component content. It has been improved. And because of the high rubber component content,
Since the effect of improving impact resistance can be obtained with a small amount, it is easy to respond to deployability. In addition, thermoplastic resins such as AS resins are excellent in productivity and low in cost. By blending them, it is possible to mass-produce low-cost ABS resins excellent in productivity.

────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Hiroo Nakamura 2--11-24 Tsukiji, Chuo-ku, Tokyo Japan Synthetic Rubber Co., Ltd. (56) References JP-A-3-177405 (JP, A) JP-A Heisei 8-319327 (JP, A) JP 46-37415 (JP, B1) (58) Fields investigated (Int. Cl. ⁷ , DB name) C08F 279/04 C08L 55/02

Claims (2)

(57) [Claims] 1. An aromatic vinyl compound (b) and a vinyl cyanide compound (c) are polymerized in the presence of a rubber-like polymer (a) component, and the content of the component (a) is from 52 to 50%.
75 % by weight, the content of the component (b) is 5 to 46 % by weight,
(C) The content of the component is 2 to 43 % by weight, and the following Q value is 12
0 × 10 ^{−4 to} 500 × 10 ⁻⁴ ml / sec, graft rate 5
A rubber-modified thermoplastic resin having a content of at least about 10% by weight. Q value: Shimadzu flow tester (CAPILLARY RH
Using EOMETER CFT-500), the volume per second (ml / sec) obtained by melting and extruding the sample under the following measurement conditions Measurement conditions: Sample amount: 1.8 g Plunger area: 1.0 cm ² die Size: 2.0 mm length × 1.0 mmφ Preheating temperature and time: 200 ° C. × 5 minutes Measurement temperature: 200 ° C. Load: 60 kg / cm ² (However, the sample to be measured is at 110 ° C. × 60 minutes. Adjust the volatile content to 0.1% by weight or less.) 2. A composition comprising the rubber-modified thermoplastic resin (A) according to claim 1 and another thermoplastic resin (B), wherein the content of the component (a) in the composition is from 3 to 35. A thermoplastic resin composition which is wt%.